JPH0629387B2 - Adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to an adhesive composition used for compounding a coated iron plate, a gypsum board, a rock wool board and the like. The composite material obtained by using the adhesive composition of the present invention is useful as a siding material, an indoor partition plate, a wall material for a unit bath, or the like.

[Conventional technology]

Composite materials such as siding materials, partition boards, and wall materials for unit baths are usually manufactured by the following method.

That is, a method in which an adhesive is uniformly applied to one or both surfaces of a substrate with a roll coater or a flow coater, and immediately one substrate is covered and adhered under a load applied at room temperature. This is a method in which the adhesive is forcibly dried and one of the base materials is laminated and combined by a roll press.

Conventionally, as the adhesive that has been used in the production of the composite material, chloroprene rubber type as a solvent type, as an aqueous emulsion type, ethylene-vinyl acetate copolymer emulsion or styrene-butadiene copolymer latex type adhesive is mainly Can be mentioned.

[Problems to be solved by the invention]

However, the solvent-type chloroprene rubber-based adhesive has problems such as safety and health, environmental pollution, and fire risk. In addition, when adopting a roll press bonding method with excellent productivity, it is necessary to apply adhesive on both sides of the substrate to develop adhesive strength, so in recent years there is no concern about fire, etc. There is a move towards using possible aqueous emulsion types.

On the other hand, in the case of an aqueous emulsion type adhesive, about half of the adhesive is usually water, so at room temperature adhesion, it takes several hours to develop the adhesive force due to the permeation of water into the substrate such as a board, which is unproductive. The demand for fast-drying adhesives is increasing. In addition, in the bonding method by forced drying, in addition to the problem of drying equipment for removing water and the cost required for drying, there are problems such as poor adhesion due to insufficient adhesiveness of the dry film of the adhesive. However, the demand for adhesives that are fast-acting, fast, and highly dry is increasing.

In addition, due to recent changes in the materials of the composite material, it has been required to further improve the performance of the adhesive in response to this.

That is, the coated iron plate is mainly embossed, and the board used as a heat insulating material is becoming a mainstream with the emergence of lightweight rock wool board or the like instead of the conventional gypsum board. Since the substrate surface of embossed products has irregularities, the adhesive area is naturally small, and it is necessary to increase the amount of adhesive applied in order to obtain the same adhesive strength as conventional flat plate coated products. . On the other hand, since rock wool board is a low-density, low-density base material, the adhesive easily penetrates into the board, and it is necessary to increase the coating amount in order to obtain stable adhesive strength. . Under such adhesion conditions, as described above, it is necessary to apply more time or heat energy to the water-based emulsion adhesive in order to develop the adhesive strength. In other words, room temperature bonding requires more and more time, and the forced drying method requires high temperature heating, which necessitates improvement in equipment. Came to be requested.

The object of the present invention is to solve problems such as safety and health, environmental pollution, risk of fire, etc., to accelerate the development of adhesive force in the production of composite materials, and to have a stable adhesive force regardless of the adhesive method. An object is to provide an aqueous emulsion type adhesive composition for chemicals.

[Means for solving problems]

In order to achieve this object, the present inventors have conducted extensive studies, and as a result, an aqueous emulsion and a styrene-butadiene copolymer latex containing a tackifying resin, a specific surfactant and a specific solvent are combined in a specific amount. They found that the matter was extremely effective, and completed the present invention.

That is, the present invention, (a) with respect to 100 parts by weight of the solid content of the aqueous emulsion, (b) styrene-butadiene copolymer latex compound containing a tackifying resin as a solid content of 5 to 100 parts by weight, (c) An adhesive composition comprising a 1% aqueous solution having a surface tension of 35 dyne / cm or less as a solid content of 0.05 to 1.0 part by weight and (d) methyl alcohol at 1 to 30 parts by weight.

As the aqueous emulsion of (a) used in the present invention,
Commercially available styrene-butadiene copolymer latex, styrene-methylmethaarylate-butadiene copolymer latex, methylmethacrylate-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, chloroprene latex, vinylidene chloride latex, vinyl chloride emulsion. , Acrylic emulsion, vinyl acetate emulsion, ethylene-vinyl acetate copolymer emulsion, ethylene-vinyl chloride copolymer emulsion, ethylene-vinyl acetate-vinyl chloride copolymer emulsion, natural rubber latex, urethane dispersion and the like.

In these aqueous emulsions, the average particle size is 0.10-0.
3μ, glass transition temperature (Tg) 0 to -30 ℃, solid content 40 to 6
It is preferably 0% and has a pH of 4 to 10. Average particle size 0.10
If it is less than μ, the drying property, that is, the film formation rate is faster, but the penetration into the board used as a heat insulating material is increased, and 0.3
If it is larger than μ, the film formation rate becomes slow and there is a practical problem. If the glass transition temperature (Tg) is higher than 0 ° C, the adhesiveness will be insufficient, causing problems with the adhesiveness in the roll press bonding method by forced drying, and if it is lower than -30 ° C, the cohesive force will be insufficient, resulting in poor heat resistance. It becomes a problem. When the solid content is 40% or less, it takes time to remove water, and it becomes difficult to achieve the object of the present invention. If it exceeds 60%, it is effective for expressing the adhesive strength, but it has an economical problem in terms of the price of the adhesive. pH 4
If it is less than the above, it may cause rust if the coated iron plate is scratched, and if it exceeds pH 10, there is a concern that there is a danger to the human body when touching the skin.

Such an aqueous emulsion is specifically adhesive strength, heat resistance, cold resistance, durability, drying property, film forming property of the film,
From the viewpoint of price, styrene-butadiene copolymer latex, styrene-methylmethacrylate-butadiene copolymer latex, methylmethacrylate-butadiene copolymer latex, and acrylic emulsion are preferable.

As a method for producing a styrene-butadiene copolymer latex compound containing a tackifying resin (b) used in the present invention, for example, a tackifying resin solution dissolved in an organic solvent is added with a small amount of a surfactant, A method of continuously adding a styrene-butadiene copolymer latex continuously under conditions of high temperature and high speed stirring can be mentioned. The viscosity of the compound thus obtained is 100 to 10,000 cps, preferably 500 to 3000 cps, and the solid content is 40 to 70%, preferably 50 to 60%.
%, PH 7-8 is a compound with excellent adhesiveness.

The tackifying resin used in the present compound, natural or polymerized rosin, rosin-based tackifying resin represented by glycerin ester of modified rosin and hydrogenated rosin, triethylene glycol ester, pentaerythritol ester, α-pinene, β- Terpene-based resins represented by polymers such as pinene, dipentene, and terpenephenol,
Examples include aliphatic petroleum-based resins, aromatic petroleum-based resins, alkylphenol resins, coumarone-indene resins, xylene resins and the like. Of these, a rosin-based resin having a softening point of the resin of 90 to 125 ° C. is particularly preferable from the viewpoint of adhesion performance.

As the surfactant used in the production of the present compound, any of the anionic and nonionic surfactants used in the emulsion polymerization of ordinary emulsions can be used, but preferably they have excellent emulsifying power and low foaming. Type H
LB 12-14 polyoxyethylene alkyl ether types are mentioned.

As the organic solvent used in the production of the present compound, basically any solvent that can dissolve the tackifying resin can be used, but toluene, n- and n- can be used because of the odor of the compound and the dry surface of the adhesive coating layer. Hexane, n-heptane,
Examples thereof include cyclohexane and ethyl alcohol, and it is desirable to use one kind or a combination of two or more kinds of these.

The styrene-butadiene copolymer latex has a copolymerization monomer ratio of styrene and butadiene of 4/6 to 6/4, and acrylic acid, methacrylic acid, itaconic acid, acrylic amide, and methylol acrylic amide as functional group monomers. , Hydroxyethyl acrylate, hydroxyethyl methacrylate, etc. glass transition temperature (Tg) 0 to -30 ° C, viscosity 50 to 10,000 cps, solid content 40
.About.70%, pH 6-9 latex. The amount of functional group monomer to be copolymerized is usually 10% by weight or less of the polymer.

The mixing ratio of each of the above is 100 to 10 parts by weight of the tackifying resin, 2 to 10 parts by weight of a surfactant, 20 to 100 parts by weight of an organic solvent, and 10 to 10 parts of a styrene-butadiene copolymer latex.
00 parts by weight is the preferred range. Particularly preferably, the amount of the surfactant used is 4 to 6 parts by weight from the viewpoint of the compound production and storage stability, and the amount of the organic solvent used is 30 to 60 parts by weight from the viscosity of the tackifying resin solution and the odor of the compound product. The amount of styrene-butadiene copolymer latex used is 300 to 6 depending on the viscosity and adhesive performance of the compound product.
A range of 00 parts by weight is desirable.

In the present invention, the purpose of blending the compound is
This is to improve the adhesive force (adhesion) by compensating for the tackiness of the aqueous emulsion used as the base resin, and to improve the drying rate due to the effect of containing an organic solvent.

Concretely showing a production example of this compound, an organic solvent, a surfactant and a tackifying resin are charged in a closed pot equipped with a stirrer, and the mixture is stirred and dissolved at room temperature to 70 to 80 ° C., and the temperature of the solution is 50 A stable compound having an average particle size of 0.2 to 0.25μ, a solid content of 50%, and a pH of 8 is obtained by a method in which the styrene-butadiene diene latex is gradually added under a high-speed stirring condition while maintaining at -60 ° C. can get.

The compound may be thickened with a water-soluble polymer, polyacrylic acid or a salt thereof, etc., if necessary.

The styrene-butadiene copolymer compound containing the tackifier resin obtained as described above has a solid content of 5 to 100 parts by weight with respect to 100 parts by weight of the solid content of the aqueous emulsion.
It is used in the range of 100 parts by weight, preferably in the range of 10 to 50 parts by weight. When the amount is less than 5 parts by weight, no remarkable improvement in drying property and adhesive strength is observed, and when the amount is more than 100 parts by weight, heat resistance and weather resistance are problematic, and particularly when used as an outer wall material, it lacks practicality.

The surface tension of the 1% aqueous solution of (C) used in the present invention is 35 dyne / cm.
The following surfactants increase the wettability of coated iron plates and the permeability of water in the adhesive to the heat insulation board,
It is intended to improve the drying property of the adhesive coating film. Examples of such a surfactant include dialkyl sulfosuccinate soda salt, acetylene alcohol, acetylene glycol, alkylnaphthalene sulfonate, polyethylene glycol nonyl phenyl ether, polyethylene glycol octyl phenyl ether, polyethylene glycol alkyl allyl ether, polyethylene glycol alkyl ether. Etc., and these can be used individually or as a mixture. A particularly preferred surfactant is an alkyl sulfosuccinate ester soda salt.

The amount of the above surfactant is in the range of 0.05 to 1.0 part by weight based on 100 parts by weight of the solid content of the aqueous emulsion, and 0.1 to 0.
A range of 5 parts by weight is preferred. If the amount is less than 0.05 parts by weight, no significant effect is observed on the adhesion to the coated iron plate and the penetration to the heat insulating board.If the amount is more than 1.0 parts by weight, the foaming, water resistance and moisture resistance are adversely affected. The effect no longer improves.

The (d) methyl alcohol used in the present invention refers to a commercially available reagent or industrial use, and is used in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the solid content of the aqueous emulsion, and particularly preferably 2 to 10 parts by weight. The range is parts by weight. The purpose of using methyl alcohol is to improve the drying rate of the adhesive coating film by blending a low boiling point solvent together with the dilution and dissolution of the ester soda salt of dialkyl succinic acid.

The adhesive composition of the present invention, for example, in a container with a stirrer
An aqueous emulsion of (a), a styrene-butadiene resin latex compound containing a tackifying resin of (b) and a surfactant of (C) diluted and dissolved in methyl alcohol of (d) were stirred in this order. Obtained by administering under conditions, if necessary by thickening with water-soluble polymer polyacrylic acid or its salt, solid content 50%, viscosity 200 cps,
A stable adhesive composition having a pH of 8 is obtained.

The adhesive composition thus obtained, in the adhesion of the composite material, the drying speed is significantly improved, the adhesiveness is also improved, room temperature adhesion method, the roll press method after forced drying adhesion method Even when it is placed on the surface, it can be bonded for a short time, the adhesive force is stabilized, and the practical value as an adhesive for composite materials is extremely high.

〔Example〕

Next, the present invention will be specifically described with reference to production examples, examples and comparative examples, but the present invention is not limited to the following examples.

In the following, parts and% are based on weight unless otherwise specified.

Production Example 1 Super ester A-115 (Arakawa Chemical Industry Co., Ltd.) was used as a rosin-based tackifying resin in a separable flask equipped with a stirrer.
Product name, softening point 110-120 ° C) 100 parts, Emulgen 910 (Kao Atlas Co., Ltd. product name, polyoxyethylene nonylphenyl ether, HLB 12.2) 8 parts as a surfactant
50 parts of toluene was charged as an organic solvent, and dissolved by stirring at 75 ° C.

Then, the solution temperature of the solution was set to 55 ° C., 30 parts of water was gradually added under high-speed stirring conditions, and then styrene-butadiene copolymer latex (manufactured by Mitsui Toatsu Chemicals, Inc., trade name). Struct bond 1351, solid content 47.5%, viscosity 150cps, pH
Slowly adding 450 parts of 8.0, Tg -27 ° C., average particle size 0.15 μ) and cooling to room temperature, a uniform and stable styrene-butadiene copolymer latex compound containing a tackifying resin was obtained. This compound is solid
The viscosity was 50%, the viscosity was 1,000 cps, and the pH was 8.0.

Example 1 As an aqueous emulsion, Struct Bond 1632 (trade name, manufactured by Mitsui Toatsu Chemicals, Inc., hydroxyl group- and acrylic acid-modified styrene-methyl methacrylate-butadiene copolymer latex, solid content 48%, viscosity 2500 cps, pH 7.0). ) 100
15 parts by weight of styrene-butadiene copolymer latex compound (hereinafter referred to as compound) containing the tackifying resin obtained in Production Example 1, 5% with methanol in advance.
3 parts of a dialkyl sulfosuccinic acid ester soda salt (hereinafter referred to as a penetrant solution) dissolved in and mixed with was mixed and stirred to obtain an adhesive composition of the present invention. The drying speed and the adhesiveness development were tested by the methods described below, and the results are shown in Table 1.

Test method 1) Drying speed a) Apply 100 g / m ² of adhesive to a colored iron plate cut into a size of 10 cm × 10 cm coated with epoxy paint, immediately cover the rock wool board of the same size as the colored iron plate, and weigh 10 kg. A dry state of the adhesive due to forced peeling after 10 minutes was put on a weight was observed and displayed as shown below.

○ …… Adhesive layer is semi-transparent or partially transparent △ …… 〃 Partially translucent × …… 〃 There is no big difference from the time of application b) Apply the adhesive to the same base material as above and apply After drying for 1 minute with a hot air dryer at ℃, the rock wool board was immediately covered, and the dried state of the adhesive at the time of forced peeling after the weight was applied for 5 minutes was observed, and the result was displayed according to the above a).

2) Adhesive strength development In the test of the drying speed test method a), the rate of the base material fracture and the depth of the material fracture remaining on the colored iron plate surface of the rock wool board during forced peeling were observed and displayed as shown below. did.

○ …… 50% or more of the total area and a depth of 2-3 mm △ …… 20-50% of the total area and a depth of 1-2 mm × …… less than 20% of the total area of the material And, the material breaking depth is 1 mm or less (a part of the surface layer) Example 2 As an aqueous emulsion, Structbond 1351 (trade name, manufactured by Mitsui Toatsu Chemicals, Inc., hydroxyl group, acrylic acid and 2-ethylhexyl acrylate modified styrene-butadiene diene copolymer) Combined latex, solid content 47.5%, viscosity 150 cps, pH 8.
0, Tg −27 ° C.) 15 parts of the compound obtained in Production Example 1 and 3 parts of the penetrant solution used in Example 1 were mixed with 100 parts of
An adhesive composition of the present invention was obtained. The same test as in Example 1 was performed and the results are shown in Table 1.

Example 3 As an aqueous emulsion, Structbond 5169EE (trade name, manufactured by Mitsui Toatsu Chemicals, Inc., acrylic emulsion, monomer composition, butyl acrylate / 2 ethylhexyl acrylate / methyl acrylate / methacrylic acid = 77)
/ 10/10/3, solid content 50%, viscosity 100 cps, pH 8.0) To 100 parts, the compound obtained in Production Example 1 was mixed with 15 parts, and the penetrant solution used in Example 1 was mixed with 3 parts. An adhesive composition of was obtained. The same test as in Example 1 is performed and the results are shown in Table-1.
It was shown to.

Example 4 As an aqueous emulsion, Polylac 520 (trade name, manufactured by Mitsui Toatsu Chemicals, Inc., methacrylic acid-modified methyl methacrylate-butadiene diene copolymer latex, solid content 47.5)
%, Viscosity 150cps, pH 7.0, Tg -28 ℃) For 100 parts,
15 parts of the compound obtained in Production Example 1 and 3 parts of the penetrant solution used in Example 1 were mixed to obtain an adhesive composition of the present invention.
The same test as in Example 1 was performed and the results are shown in Table 1.

Example 5 Structbond 1632, 100 as an aqueous emulsion
5 parts of the compound obtained in Production Example 1 and 3 parts of the penetrant solution used in Example 1 were blended with 3 parts to obtain an adhesive composition of the present invention.

The same test as in Example 1 was performed below, and the results are shown in Table 1.

Example 6 As an aqueous emulsion, struct bond 1632, 100
To the parts, 96 parts of the compound obtained in Production Example 1 and 3 parts of the penetrant solution used in Example 1 were blended to obtain an adhesive composition of the present invention.

The same test as in Example 1 was performed below, and the results are shown in Table 1.

Example 7 Structbond 1632, 100 as an aqueous emulsion
15 parts of the compound obtained in Production Example 1 and 9.5 parts of the penetrant solution used in Example 1 were mixed with the parts to obtain an adhesive composition of the present invention.

The same test as in Example 1 was performed below, and the results are shown in Table 1.

Example 8 Structbond 1632, 100 as an aqueous emulsion
15 parts of the compound obtained in Production Example 1 and 0.5 part of the penetrant solution used in Example 1 were mixed with the parts to obtain an adhesive composition of the present invention.

The same test as in Example 1 was performed below, and the results are shown in Table 1.

Comparative Example 1 Struct Bond 1632 was subjected to the same test as in Example 1,
The results are shown in Table-1.

Comparative Example 2 15 parts of the compound obtained in Production Example 1 was mixed with 100 parts of Structbond 1632, and the mixture was subjected to the same test as in Example 1 below. The results are shown in Table 1.

Comparative Example 3 100 parts of Struct Bond 1632 was mixed with 3 parts of the penetrant solution used in Example 1, and the same test as in Example 1 was performed. The results are shown in Table 1.

[Effects of the Invention] As is clear from Table 1, the adhesive composition of the present invention is free from the concerns of safety and health, environmental pollution, fire, etc., and moreover, it is a conventional aqueous emulsion system for bonding composite materials. The drying speed and adhesive force development, which were not achieved with adhesives, are remarkably improved, and stable adhesive force can be obtained in a short time regardless of the adhesive method.Therefore, practical value as an adhesive for composite materials is extremely high. It is high and its significance is great.

Claims (1)

[Claims] 1. A solid content of (a) 100 parts by weight of an aqueous emulsion, 5 to 100 parts by weight of (b) a styrene-butadiene copolymer latex compound containing a tackifying resin, and (c) 1 % Aqueous solution having a surface tension of 35 dyne / cm or less in a solid content of 0.05 to 1.0 part by weight, and (d) methyl alcohol in an amount of 1 to 30 parts by weight.